WO1992007255A1 - Method for detection of alien matter contents in gases - Google Patents

Method for detection of alien matter contents in gases Download PDF

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Publication number
WO1992007255A1
WO1992007255A1 PCT/FI1991/000312 FI9100312W WO9207255A1 WO 1992007255 A1 WO1992007255 A1 WO 1992007255A1 FI 9100312 W FI9100312 W FI 9100312W WO 9207255 A1 WO9207255 A1 WO 9207255A1
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Prior art keywords
ions
channel
positive
different
edge
Prior art date
Application number
PCT/FI1991/000312
Other languages
French (fr)
Inventor
Pertti Puumalainen
Original Assignee
Puumalainen Consults Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Puumalainen Consults Oy filed Critical Puumalainen Consults Oy
Priority to EP91917494A priority Critical patent/EP0552206B1/en
Priority to DE69126711T priority patent/DE69126711D1/en
Priority to JP3516103A priority patent/JPH06507472A/en
Publication of WO1992007255A1 publication Critical patent/WO1992007255A1/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
    • G01N27/66—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber and measuring current or voltage

Definitions

  • the object of the invention is a method for detection of alien matter contents in gases, in which method the gas is first ionized and alien matters are detected and determined by the bahaviour of formed ions.
  • Alien matter contents are often detected and determined in order to control that the air is safe to breath.
  • Particu ⁇ larly when analyzing certain very poisonous substances, which appear in small quantities, other substances of air may disturb detection.
  • the quantities of different sub- stancies, such as carbon dioxide, may vary in air.
  • the detection of different molecules or molecule groups from gases or vapour of vaporized solid or liquid materials is often connected with problems.
  • detection of poisonous substances, such as nerve gases spread in the air, reliably and fast enough from small quantities is diffi ⁇ cult. The detection should be made in a few seconds and, with the most effective nerve gases, from concentrations as small as 1/100 ppm.
  • the most sensitive analyzing devices are based on ionizing the air for example by alfa or beta radiation and measuring the ions in different circumstances.
  • the ions are made to penetrate through a certain kind of a labyrinth and the remaining ions are measured from the current they generate.
  • Another method observes the mobi ⁇ lity of the ions through different grids and finally ion current is measured.
  • very heavy mole ⁇ cules such as most combat gases, can be detected from air.
  • ionized molecules are led through chambers, which have different electric fields, and the nature and concentration of the molecules of alien matters are tried to be detected by measuring the current from these electric fields. This method is rather efficient, but the recombina ⁇ tion of different charges is a problem, because it makes ions disappear faster.
  • the aim of the invention is to bring about a method for the detection of alien matter contents in gases, by which the nature and quantity of different alien matter components in a gaseous state are measured and detected, even small con ⁇ centrations, such as below 1 ppm.
  • the purpose of the invention is to bring forth a method, by which the consistency and quantity of nerve gases or other similar gases can be detected quickly and early.
  • the gas and the different substances contained in it are ionized in a ionization room by applicable radiation, for instance by alfa radiation.
  • the gas is transferred into a separating part, where the ions in the gas are separated into positive and negative ions.
  • At least the ions with one sign are led into a narrow analyzing channel, in which they are forced to move in the middle section of the channel because of the capillary force. From here they are taken by electric fields of different strength to an electrode located at the edge of the channel, where they cause ion current.
  • a current spec ⁇ trum is calculated, from which different substances are detected and their concentrations determined with the aid of corresponding spectra calculated from standard samples of different substances.
  • the analyzing channels are made narrow, so the ions move in them without losses, even distances of several tens of meters, especially when they are well separated from the ions with opposite sign.
  • This is the so called capillary transportation, which is known from some ion transportation equipments used in nuclear physics.
  • the ions are deflected with different electric fields away from the carrier gas, small and highly charged ions or particles are deflected by a low voltage, while large molecules or particles with a small charge require a high voltage.
  • x-axis is the voltage from negative (deflection of positive ions) to positive (deflection of negative ions)
  • y-axis is the ion current measured from corresponding deflection spot. From this spectrum different substances can then be detected based on the spectra of standard samples.
  • the method is functioning in atmospheric pressure or in underpressure.
  • the air can be filtered mechanically before the analysis or, for example moisture can be removed. Often the air is also heated in order to vaporize the aerosol particles contained in it. If liquids are analyzed, they are first brought into a gaseous state by lowering the pressure and/or heating.
  • positive ions are deflected to one edge and negative ions to the other edge of the separation section by a magnetic field per- pendicular to the direction of the gas flow. Also, absorb- tion of the ions, which have been forced to the edge of the channel in the separation section, is prevented by charging the wall with a charge whose sign is equal to the charge of the ion.
  • the ions are separated into positive and negative by an electric field across the separation section, in which case the positive ions go towards one edge and the negative ions towards the other edge. In some embodiments one or more electric fields can be used and/or electric and magnetic fields at the same time.
  • successive grids are placed into the channels, which are branched off from the channel that goes through the separation section, and the voltage in these grids increases from one grid to the next in positive direction in a channel for negative ions and in negative direction in a channel for positive ions. This way the flow is made more effective.
  • figure 1A presents a device system for the application of the method in accordance with the invention in cross-section and seen from the side
  • figure IB presents a current spectrum obtained by a device system presented in figure 1A.
  • the gas 7,which is led into the device system, is continuously ionized in the chamber 1 by an alfa radiation source.
  • the gas is led into the separation section 2, where it is separated by one or more electric fields or by electric and magnetic fields together so that the negative ions in this embodiment are taken to the left and the positive ions are taken to the right into the analyzing channels 3 and 4.
  • the ions are deflected by different electric fields, caused by voltages Ui-U 5 in the channels for negative ions, and we can measure positive ion currents I J -I B .
  • ions are deflected by electric fields caused by voltages U 6 -U 10 , and we can measure ion currents I 6 -I 10 .
  • the voltages in the channels can vary as wanted, and also the lengths of the electric fields.
  • the height of the channel must, however, be such, that the so called capillary forces have a strong effect on the ions, that is the ions tend to move along the center of the channel. In other words, ' ' the height of the channel is preferably less than 1 mm. From the analyzing channels the gas is sucked through the air pumps 5 and 6 away from the device system.
  • Figure IB presents a current spectrum obtained from measurements.
  • a different spectrum is always obtained with different molecules.
  • different substances are recognized and their concentrations in the gas are determined.
  • the corresponding spectra obtained by measurements with standard samples of different substances are used. If the strengths of the fields are appropriately changed, differencies between differing molecule groups can be emphasized and for example different nerve gases can be detected.
  • the invention is not limited to the presented example of usage, but it can further more be used in many other embodiments besides analyzing of air. Such embodiments are for example monitoring of industrial processes, where different molecules are recognized in the detectors of different chromatographs, such as liquid and gas chromato- graphs.
  • chromatographs such as liquid and gas chromato- graphs.
  • the amount and values of the electric fields, and also the geometry of the device, can be varied unlimitedly.
  • two or more analyzing channels can be used, in which case also the ratios between the currents caused by ions deflected in different electric fields are measured.
  • the separator section can also be different, the main thing is, that it separates the ions for the most part into positive and negative.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The objective of the invention is a method for detection of alien matter contents in gas, in which method the gas and the substances contained in it are ionized in an ionization room (1). By the present methods impurities in gases cannot be determined fast and in small concentrations. In the method of the invention the ions contained in the gas are separated in a separation section (2) into positive and negative ions, of which at least the ions of either sign are led into a narrow analyzer channel (4). There, due to the capillary force, they are be forced to move in the middle section of the channel, from where they are deflected by electric fields of different strength caused by different voltages (U1-U10) into an electrode located at the edge of the channel, where they cause ion current (I1-I10). On the basis of the ion currents a current spectrum is made, on the basis of which different substances are detected and their concentrations determined with the aid of corresponding spectra obtained with standard samples of different substances.

Description

METHOD FOR DETECTION OF ALIEN MATTER CONTENTS IN GASES
The object of the invention is a method for detection of alien matter contents in gases, in which method the gas is first ionized and alien matters are detected and determined by the bahaviour of formed ions.
Alien matter contents are often detected and determined in order to control that the air is safe to breath. Particu¬ larly, when analyzing certain very poisonous substances, which appear in small quantities, other substances of air may disturb detection. The quantities of different sub- stancies, such as carbon dioxide, may vary in air. The detection of different molecules or molecule groups from gases or vapour of vaporized solid or liquid materials is often connected with problems. Particularly, detection of poisonous substances, such as nerve gases spread in the air, reliably and fast enough from small quantities, is diffi¬ cult. The detection should be made in a few seconds and, with the most effective nerve gases, from concentrations as small as 1/100 ppm.
At present the most sensitive analyzing devices are based on ionizing the air for example by alfa or beta radiation and measuring the ions in different circumstances. In one method, the ions are made to penetrate through a certain kind of a labyrinth and the remaining ions are measured from the current they generate. Another method observes the mobi¬ lity of the ions through different grids and finally ion current is measured. By these two methods very heavy mole¬ cules, such as most combat gases, can be detected from air. In one method ionized molecules are led through chambers, which have different electric fields, and the nature and concentration of the molecules of alien matters are tried to be detected by measuring the current from these electric fields. This method is rather efficient, but the recombina¬ tion of different charges is a problem, because it makes ions disappear faster.
The aim of the invention is to bring about a method for the detection of alien matter contents in gases, by which the nature and quantity of different alien matter components in a gaseous state are measured and detected, even small con¬ centrations, such as below 1 ppm. In particular the purpose of the invention is to bring forth a method, by which the consistency and quantity of nerve gases or other similar gases can be detected quickly and early.
The aim of the invention is achieved by a method, the char¬ acteristics of which are presented in the claims.
In the method according to the invention the gas and the different substances contained in it are ionized in a ionization room by applicable radiation, for instance by alfa radiation. After this the gas is transferred into a separating part, where the ions in the gas are separated into positive and negative ions. At least the ions with one sign are led into a narrow analyzing channel, in which they are forced to move in the middle section of the channel because of the capillary force. From here they are taken by electric fields of different strength to an electrode located at the edge of the channel, where they cause ion current. On the ground of the ion currents a current spec¬ trum is calculated, from which different substances are detected and their concentrations determined with the aid of corresponding spectra calculated from standard samples of different substances. The analyzing channels are made narrow, so the ions move in them without losses, even distances of several tens of meters, especially when they are well separated from the ions with opposite sign. This is the so called capillary transportation, which is known from some ion transportation equipments used in nuclear physics. In the capillary space the ions are deflected with different electric fields away from the carrier gas, small and highly charged ions or particles are deflected by a low voltage, while large molecules or particles with a small charge require a high voltage. When this is done in both channels, we get a spectrum, in which for example x-axis is the voltage from negative (deflection of positive ions) to positive (deflection of negative ions), and y-axis is the ion current measured from corresponding deflection spot. From this spectrum different substances can then be detected based on the spectra of standard samples.
The method is functioning in atmospheric pressure or in underpressure. The air can be filtered mechanically before the analysis or, for example moisture can be removed. Often the air is also heated in order to vaporize the aerosol particles contained in it. If liquids are analyzed, they are first brought into a gaseous state by lowering the pressure and/or heating.
In a favourable embodiment of the invention positive ions are deflected to one edge and negative ions to the other edge of the separation section by a magnetic field per- pendicular to the direction of the gas flow. Also, absorb- tion of the ions, which have been forced to the edge of the channel in the separation section, is prevented by charging the wall with a charge whose sign is equal to the charge of the ion. In another favourable embodiment of the invention the ions are separated into positive and negative by an electric field across the separation section, in which case the positive ions go towards one edge and the negative ions towards the other edge. In some embodiments one or more electric fields can be used and/or electric and magnetic fields at the same time.
In one favourable embodiment successive grids are placed into the channels, which are branched off from the channel that goes through the separation section, and the voltage in these grids increases from one grid to the next in positive direction in a channel for negative ions and in negative direction in a channel for positive ions. This way the flow is made more effective.
In the following the invention is explained more in detail by referring to the attached drawing, in which figure 1A presents a device system for the application of the method in accordance with the invention in cross-section and seen from the side, and figure IB presents a current spectrum obtained by a device system presented in figure 1A.
In the embodiment presented in figure 1A the gas 7,which is led into the device system, is continuously ionized in the chamber 1 by an alfa radiation source. After this the gas is led into the separation section 2, where it is separated by one or more electric fields or by electric and magnetic fields together so that the negative ions in this embodiment are taken to the left and the positive ions are taken to the right into the analyzing channels 3 and 4. In the analyzing channels the ions are deflected by different electric fields, caused by voltages Ui-U5 in the channels for negative ions, and we can measure positive ion currents IJ-IB. In the analyzing channels for positive ions, ions are deflected by electric fields caused by voltages U6-U10, and we can measure ion currents I6-I10. The voltages in the channels can vary as wanted, and also the lengths of the electric fields. The height of the channel must, however, be such, that the so called capillary forces have a strong effect on the ions, that is the ions tend to move along the center of the channel. In other words, '' the height of the channel is preferably less than 1 mm. From the analyzing channels the gas is sucked through the air pumps 5 and 6 away from the device system.
Figure IB presents a current spectrum obtained from measurements. In principle, a different spectrum is always obtained with different molecules. On the basis of the current spectrum, different substances are recognized and their concentrations in the gas are determined. In this the corresponding spectra obtained by measurements with standard samples of different substances are used. If the strengths of the fields are appropriately changed, differencies between differing molecule groups can be emphasized and for example different nerve gases can be detected.
The invention is not limited to the presented example of usage, but it can further more be used in many other embodiments besides analyzing of air. Such embodiments are for example monitoring of industrial processes, where different molecules are recognized in the detectors of different chromatographs, such as liquid and gas chromato- graphs. The amount and values of the electric fields, and also the geometry of the device, can be varied unlimitedly.
For the positive and/or negative ions two or more analyzing channels can be used, in which case also the ratios between the currents caused by ions deflected in different electric fields are measured. The separator section can also be different, the main thing is, that it separates the ions for the most part into positive and negative.

Claims

1. Method for determining of alien mateer content, in which method the gas and the substances contained in it are ionized in an ionization room (1), c h a r a c t e r i ¬ z e d in, that the ions contained in the gas are separated in a separation section (2) into positive and negative ions, of which at least the ions of either sign are led into a narrow analyzer channel (4), where they will, due to the capillary force, be forced move in the middle section of the channel, from where they are deflected by electric fields of different strengths caused by different voltages (Ut-U5) and (U6-U10) into an electrode at the edge of the channel, where they cause ion current (Iι-I5) and (I6 -Ix0) and that on the basis of the ion currents a current spectrum is made on the basis of which different substances are recognized and their concentrations determined with the aid of corresponding spectra obtained with standard samples of different substances.
2. Method according to claim 1, c h a r a c t e r i z e d in, that in the separation section (2) the positive ions are deflected to one edge and the negative ions to the other edge by a magnetic field perpendicular to the direction of the gas flow and absorbtion of ions which have been forced to edge by charging the wall with a charge of same sign as the ion has.
3. Method according to claim 1, c h a r a c t e r i z e d in, that as the channel of the separation section (2) branches, successive grids are placed into the branch channels, in which grids the voltage rises to positive direction in a channel for negative ions and to negative direction in a channel for positive ions when moving from one grid to the next.
4. Method according to claim 1, c h a r a c t e r i z e d in, that in the separation section (2) the ions are separated into positive and negative ions by a crosswise electric field, so the positive ions will move towards one edge of the channel in the separation section, and the negative ions towards the othe edge.
5. Method according to some of claims 1-4, c h a r a c e¬ r i z e d in, that at least two analyzer channels are used for both negative and positive ions, in which case also the relations between currents caused by ions deflected in different electric fields are measured.
PCT/FI1991/000312 1990-10-11 1991-10-10 Method for detection of alien matter contents in gases WO1992007255A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP91917494A EP0552206B1 (en) 1990-10-11 1991-10-10 Method for detection of alien matter contents in gases
DE69126711T DE69126711D1 (en) 1990-10-11 1991-10-10 METHOD FOR DETERMINING FOREIGN BODY CONTENT IN GASES
JP3516103A JPH06507472A (en) 1990-10-11 1991-10-10 Method for detecting foreign substances in gas

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI904997A FI87954C (en) 1990-10-11 1990-10-11 Procedure for determining gas content of ingredients
FI904997 1990-10-11

Publications (1)

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WO1992007255A1 true WO1992007255A1 (en) 1992-04-30

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US (1) US5543331A (en)
EP (1) EP0552206B1 (en)
JP (1) JPH06507472A (en)
AT (1) ATE154978T1 (en)
AU (1) AU8643791A (en)
CA (1) CA2093657A1 (en)
DE (1) DE69126711D1 (en)
FI (1) FI87954C (en)
WO (1) WO1992007255A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020845A1 (en) * 1993-03-05 1994-09-15 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Gas detection devices
WO1996018893A1 (en) * 1994-12-15 1996-06-20 Environics Oy Method for measurement of analytes by ion mobility spectrometry
WO2003081224A1 (en) * 2002-03-25 2003-10-02 Lappeenrannan Teknillinen Yliopisto A cell structure, device and methods for gas analysis

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001095999A1 (en) * 2000-06-09 2001-12-20 University Of Delaware System and method for chemical analysis using laser ablation
US6606899B1 (en) * 2000-07-07 2003-08-19 Air Products And Chemicals, Inc. Total impurity monitor for gases
US9390898B1 (en) * 2013-08-30 2016-07-12 Leidos, Inc. System and method for fusing chemical detectors
CN104569233B (en) * 2013-10-28 2018-04-24 同方威视技术股份有限公司 ion mobility spectrometer system
CN109841471B (en) * 2017-11-24 2021-12-17 北京北方华创微电子装备有限公司 Device for separating positive ions from negative ions, film forming equipment and chamber cleaning method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2422264A (en) * 1945-05-08 1947-06-17 Robert V Seaman Differential ionic analyzer
EP0027748A1 (en) * 1979-10-01 1981-04-29 The Bendix Corporation Ion mobility detector for either simultaneous or sequential detection of positive and negative ions
WO1987007720A1 (en) * 1986-06-03 1987-12-17 Pertti Puumalainen Method for detection of alien matter contents in gases
WO1990009583A1 (en) * 1989-02-09 1990-08-23 Graseby Ionics Limited Ion mobility detector

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4445038A (en) * 1979-10-01 1984-04-24 The Bendix Corporation Apparatus for simultaneous detection of positive and negative ions in ion mobility spectrometry

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2422264A (en) * 1945-05-08 1947-06-17 Robert V Seaman Differential ionic analyzer
EP0027748A1 (en) * 1979-10-01 1981-04-29 The Bendix Corporation Ion mobility detector for either simultaneous or sequential detection of positive and negative ions
WO1987007720A1 (en) * 1986-06-03 1987-12-17 Pertti Puumalainen Method for detection of alien matter contents in gases
WO1990009583A1 (en) * 1989-02-09 1990-08-23 Graseby Ionics Limited Ion mobility detector

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020845A1 (en) * 1993-03-05 1994-09-15 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Gas detection devices
GB2291712A (en) * 1993-03-05 1996-01-31 Secr Defence Gas detection devices
US5701009A (en) * 1993-03-05 1997-12-23 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Of Defence And Evaluation Research Agency Gas detection devices
WO1996018893A1 (en) * 1994-12-15 1996-06-20 Environics Oy Method for measurement of analytes by ion mobility spectrometry
WO2003081224A1 (en) * 2002-03-25 2003-10-02 Lappeenrannan Teknillinen Yliopisto A cell structure, device and methods for gas analysis
US7339162B2 (en) 2002-03-25 2008-03-04 Environics Oy Cell structure, device and method for gas analysis
US7586090B2 (en) 2002-03-25 2009-09-08 Environics Ov Cell structure, device and method for gas analysis

Also Published As

Publication number Publication date
FI904997A (en) 1992-04-12
JPH06507472A (en) 1994-08-25
FI87954B (en) 1992-11-30
ATE154978T1 (en) 1997-07-15
FI904997A0 (en) 1990-10-11
AU8643791A (en) 1992-05-20
FI87954C (en) 1999-03-23
DE69126711D1 (en) 1997-08-07
EP0552206A1 (en) 1993-07-28
US5543331A (en) 1996-08-06
CA2093657A1 (en) 1992-04-12
EP0552206B1 (en) 1997-07-02

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